DE3245467A1 - POLYCARBONATE RESIN - Google Patents

Description

The invention relates to a polycarbonate resin composition with improved properties, which a polycarbonate resin, an aromatic polyester resin and a modifying resin. In particular, the invention relates to a Polycarbonate resin composition with improved properties such as excellent resistance to solvents, especially gasoline, especially gasoline with a high cetane number, excellent impact resistance, especially at low temperatures, resistance to damage heat aging impact resistance, improved melt flow property, and excellent mold releasability in a well-balanced combination during shaping.

In particular, the invention relates to a polycarbonate resin composition the end

(A) 20 to 90% by weight of a polycarbonate resin,

(B) 5 to 70% by weight of an aromatic polyester resin,

(C) 1 to 15% by weight of an isobutylene copolymer rubber, the one from a larger proportion of isobutylene and one

20 smaller proportion of isoprene is built up,

(D) 1 to 20% by weight of an elastomeric acrylic graft copolymer resin, which is made of a crosslinked acrylic copolymer with a content of not less than 3 wt.% Butadiene as a comonomer, which is free from ethylene, as a parent polymer and at least one grafted onto it Graft monomers from the group of styrene, alkyl aerylates and alkyl methacrylates, and

(E) 0 to 15% by weight of a mixture derived from an olefin 2 to 6 carbon atoms derived olefin resin, the weight ratio of [Resin (A) + Resin (B)] / [Rubber (C) + Resin (D)] is 2 to 20, and if so the resin (E) is present, the weight ratio of Resin (B) / [rubber (C) + resin (D) + resin (E)] is 1 to 5.

Exterior motor vehicle parts such as shock absorbers, panels - and Katflügel were previously made of steel, but now occurred due to the need to reduce fuel costs and the weight of automobiles, there is a strong need for the Use of plastics as a substitute for steel. The advantages of plastic such as high corrosion resistance and buckling resistance to steel are still valued, and a special one Interest arose in folycarbonate resins with their excellent impact resistance and Heat resistance. '-

: ■ When used as automotive component parts show the molded articles made of polycarbonate resins following four problems:

1) The impact resistance of a molded article a polycarbonate resin depends largely on it. Thickness from. For example, shows the notched Izod impact value a 3.2 mm thick object a plastic crack, while a 6.4 mm thick object shows a brittle crack. This shows that the impact resistance is strong for an object with a large Thickness is reduced.

2) The high Izod strength (notched impact strength) at a thickness of 3.2 mm decreases rapidly at low

Temperatures. -

3) If the polycarbonate article is exposed to high temperature conditions, it shows heat aging and greatly decreases in impact resistance, -4) Due to a low solvent resistance, a large-sized article or molded article of complex shape with high residual stress develops stress cracks on contact with paints or gasoline.

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In particular, the above under 4) must Resistance to solvents and the heat aging resistance listed under 3) above Impact resistance can be greatly improved.

Various polycarbonate resin compositions, particularly those made of a polycarbonate resin, have been used and an aromatic polyester resin, optionally together with a modifying resin, even in attempts to improve the impact resistance of polycarbonates without any significant deterioration suggested its favorable properties. However, it is extremely difficult to make a polycarbonate resin composition to develop which has satisfactorily improved properties in a well-balanced combination.

For example, US Pat. No. 3,218,372 describes a resin composition which consists essentially of 95 to 5% by weight of a polycarbonate and 5 to 95% by weight of a polyalkylene terephthalate exists, and it is found that this resin composition inherently leads to easier molding. operation due to their lower melt viscosity than in the case of the single application of the polycarbonate and that, since the ductility of the resin composition is higher than in the In the case of the single application of the polyalkylene terephthalate, a molded article with excellent physical, chemical and electrical properties. However, the teaching of this patent gives nothing for the combined use of components (C), (D) and (E) in the compositions according to the present invention. The resin compositions proposed in this patent specification have unsatisfactory impact resistance, in particular at low temperatures, and do not have good resistance to solvents or good impact resistance

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sturdiness in a well-balanced combination. Also have the resin compositions described therein have an unsatisfactory resistance to damage to the impact strength Heat aging and an unsatisfactory mold release ability during shaping. ■

U.S. Patent 4,264,487 describes a high impact, durable and long term heat resistant wet composed of (a) about 25 to 95% of an aromatic polyester, (b) about 1 to 50% of an aromatic polycarbonate, and (c) the remainder to 100% % consists of a core-shell polymer, which consists of about 25 to 95% by weight of a first elastomeric phase, which consists of a monomer system of about 75 to 99.8% by weight of a (C 1 -C 6) -alkyl acrylate, 0.1 polymerized to 5 % of a crosslinking monomer and 0.1 to 5 % of a grafting monomer, and comprises about 75 to 5% of a final rigid thermoplastic phase. The combined use of components (C), (D) and (E), as used in the compositions according to the invention, cannot be derived from this patent specification. In the case of the compositions described in this patent specification, improved properties over a composition consisting essentially of the polycarbonate resin and the aromatic polyester resin are obtained by the incorporation of the core-shell polymer. However, the obtained composition still has unsatisfactory solvent resistance and unsatisfactory impact resistance at low temperature.

U.S. Patent No. 3,864,428 discloses a thermoplastic resin composition which comprises a) 25 to 85 wt.% Of an aromatic polyester, B) 10 to 75 wt. # Of aromatic polycarbonate and C) "2 to 35 wt.% Of a Pfropfcopolyroeren from a Butadiene polymer vinyl monomers, wherein

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the proportion of the butadiene polymer component in the graft polymer 1 to 30% by weight, based on the total weight of components (A), (B) and (C). These too The patent gives no indication of the combined use of components (C), (D) and (E) in the compositions according to the present invention. Furthermore, these resin compositions have further improvements in terms of Solvent resistance and impact resistance at low temperature are necessary.

In US Pat. No. 4,257,937, modified thermoplastic polyester compositions are described which (a) a Poly (1,4-butylene terephthalate) resin or a polyester copolymer and optionally a poly (ethylene terephthalate) resin and (b) as a modifier therefor, a combination of a polyacrylate resin and an aromatic polycarbonate and optionally (c) fillers and / or Contain reinforcing agents and / or (d) flame retardants. The modifier (b) provides increased Resistance to impact fracture, increased strength and improved resistance to heat deformation of molded articles produced from the masses. This patent also does not describe the combined one Application of components (C), (D) and (E) corresponding to the compositions according to the present invention, the there Compounds not entirely satisfactory in terms of solvent resistance and impact resistance are at low temperature.

Extensive studies were carried out within the scope of the invention in order to avoid the defects of the above conventional polycarbonate resin compositions made from a Pclycarbonate resin, an aromatic polyester resin and a modifying resin built to make new and

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to obtain valuable polycarbonate resin compositions, which for Obtaining molded articles with excellent resistance to solvents, especially gasoline of high octane number, and high impact resistance even in a cold atmosphere.

It was found important to be able to release the form to improve, as a poor releasability stresses in the molded articles at the time Release of the same causes the kest tension in to reduce the size of the molded articles and to prevent gasoline from entering the molded articles Studies on the basis of this finding have been undertaken to develop polycarbonate resin compositions, the larger proportion of polycarbonate and aromatic polyester which meet the above requirement and have improved properties in a more balanced manner Own combination. These investigations have now led to the finding that a polycarbonate resin mas.se from the four components (A), (B), (C) and (D) and optionally the component (E) in the above proportions as the main components exhibits excellent durability excellent impact resistance to solvents, especially high-octane gasoline, especially at low temperatures, excellent resistance to damage to impact strength due to heat aging and improved Melt flow property and excellent mold release ability during molding in a well balanced Combination owns.

The polycarbonate resin compositions according to the invention have a much higher resistance to solvents, for example, high octane gasoline, and a far greater resistance to damage to the Impact resistance by heat aging than polycarbonate resins alone, and impact resistance, in particular at low temperatures, of molded articles made of this mass with a large wall thickness, is improved. Further the compositions according to the invention have excellent moldability and give molded articles excellent mechanical properties such as tensile strength, excellent surface appearance and excellent durability against discoloration due to heat. As a result, the molded articles can be made from the compositions of the invention as external motor vehicle parts such as bumpers, Fairings and fenders are used.

It is therefore an object of the invention to provide a four-part or five-part polycarbonate resin composition with excellent improved properties. -

The foregoing and other objects of the invention and the advantages of the invention will be apparent from the following Description.

The polycarbonate resin composition according to the invention is composed of the following four or five components, of which the polycarbonate resin and the aromatic polyester resin the main components are:

(A) 20 to 90% by weight, preferably 40 to 80% by weight of a polycarbonate resin.

(B) 5 to 70% by weight , preferably 10 to 45% by weight, of an aromatic polyester resin.

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(C) 1 to 15% by weight, preferably 2 to 12% by weight an isobutylene copolymer rubber composed of a major proportion of isobutylene and a minor proportion of isoprene.

■ ". (D) 1 to 20 Gew.?S, preferably 3 to 15 wt.% Of an elastomeric Acrylpfropfcopolymerharzes that of a crosslinked acrylic copolymer having a content of not less than 3 Oev.% Butadiene as a comonomer containing crosslinked acrylic copolymer is free of ethylene, is built up as a parent polymer and grafted on at least one graft monomer from the group of styrene, alkyl acrylates and alkyl methacrylates.

(E) 0 to 15% by weight, preferably 0 to 10% by weight one is from an olefin having 2 to 6 carbon atoms derivative olefin resin.

In the above composition, the weight ratio of [Resin CA) + Resin (B)! / [Rubber (G) + Resin (D)] is 2 to 20, and if the Resin (E) is present, it is; Weight ratio of resin (B) / [rubber (G) + resin (D) + resin (E)} 1 to 5. If the resin (E) is used, its preferred amount is 1 to 10% by weight, more preferably 2 up to 3 wt. 50.

The excellent and improved properties of the folycarbonate resin compositions according to the invention are believed to be by the interaction of the four or five components listed above in the specific proportions achieved, but details of this mechanism have not yet been clarified. The above assumption guides differ from the fact that, as shown in the following comparative tests, the excellent

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improved properties cannot be obtained, if compounds are used which are missing even one of the three components (B) to (D).

The polycarbonate resin compositions according to the invention have a superior mold release ability ^ keifc and v © i'b # §g§f * te enamel properties. Therefore g-le can be too large in shape or intricately shaped objects with low residual stress. As these molded objects maintain high impact resistance even in cold atmosphere and greatly improved solvent resistance they do not suffer from stress cracking on contact with high octane gasoline and withstand blows in cold climates completely. As a result, the polycarbonate resin compositions according to FIG Invention widely used in applications requiring resistance to gasoline and require the like, for example as automotive parts. They can be particularly beneficial as motor vehicle bumpers are used where impact strength

20 speed is required in cold climates.

The polycarbonate resin (A) used in the invention can be prepared by processes known per se, for example by reacting a dihydric phenol with a carbonate precursor such as phosgene in the presence of an acid acceptor and a control agent for the Molecular weight or by ester interchange reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate.

Preferred dihydric phenols are bisphenols and bisphenol A, i.e. 2,2-bis (4-hydroxyphenyl) propane, becomes particularly preferred. Bisphenol A can be partially or completely replaced by other dihydric phenols.

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Examples of other dihydric phenols besides bisphenol A include hydroquinone, 4,4 ^I -dihydroxydiphenyl,
Bis (4-hydroxyphenyl) methane, 1,1-bis (^ -hydroxyphenyl) cyclohexane, 2,2-bis (3,5-dimethy1-4-hydroxyphenyl) propane,
Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfon ₅ , bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether and halogenated bisphenols such as 2,2-bis ( "3,5-dibromo-4-hydroxyphenyl) propane.

Bas polycarbonate resin can also be a homopolymer
of such a dihydric phenol, a copolymer

from two or more such dihydric phenols or a mixture of such polymers and / or copolymers
be. - - - -

These polycarbonate resins are easily available industrially.

Examples of preferred polycarbonate resins as component (A) are polycarbonates of bisphenol A, copolycarbonates of bisphenol A and not more than 20 MoX-Ji,
based on the total dihydric alcohol component,

of bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, Bis (4-hydroxyphenyl) sulfone, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and mixtures of bisphenol A polycarbonates with no more than 20% by weight, based on the entire mixture of a homopolycarbonate of bis (4-hydroxyphenyl) methane, 1, ί «bis (4-hydroxyphenyl) cyclohexane, Bis (4-hydroxyphenyl) sulfone, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 2,2-bis (3> 5-dibromo-4-hydroxyphenyl) propane. The bisphenol A polycarbonates are special preferred.

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The aromatic polyester resin (B) used in the present invention can be produced by a known method or can be obtained commercially. The preferred aromatic polyester resins (B-) are polyesters, which differs from an alkylene glycol with 2 to 10 carbon atoms and an aromatic diacid with 8 up to 12 carbon atoms or an ester-forming derivative derived from this, such as a lower alkyl ester of aromatic dicarboxylic acid. Examples of alkylene glycols are ethylene glycol, 1, A-butanediol, 1,6-hexanediol, 1,4-Cyclohexanedimethanol and 1, 10-decamethylene glycol, and Examples of aromatic dicarboxylic acids are terephthalic acid, isophthalic acid and 2,6-naphthalic acid. Thus, illustrative examples of such aromatic polyester resins (B) are poly (ethylene terephthalate), poly (1,4-butylene terephthalate), amorphous poly (ethylene terephthalate) * copolyester, amorphous poly (I, ^ - butylene terephthalate) copolyester and amorphous poly (1,4-cyclohexanedimethylene terephthalate) copolyester.

A copolymer commonly referred to as "butyl rubber" can be used as isobutylene copolymer rubber (C) in the compositions according to the invention. It consists, for example, of a copolymer rubber made up of 93 to 99% by weight isobutylene and 7 to 1% by weight isoprene. Such copolymer rubbers and methods for their preparation are known and the copolymer rubber is commercially available. The Isobutylencopolymerkautschuk (C) may, for example, by copolymerizing 93 to 99 wt.% Isobutylene and 7 to 1 wt. ^ Isoprene in the presence of a Friedel-Cr-AFTS-Metallhalogenickatalysators such as aluminum chloride at a low temperature, for example about -100 ⁰ C, are prepared . Before-

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preferably, the copolymer rubber (C) has a relative high melt viscosity. Examples of commercially available copolymer rubbers (C) are IIR-065 and "IIK-268 (Products of Nippon Butyl Co., Ltd.) and Exxon Butyl-O65 (Product of Exxon Chemical Co.).

The elastic acrylic graft copolymer used according to the invention as component (D) is composed of a composite. networked acrylic copolymers which contain not less than 3 wt.%, preferably 3 to 40 wt. %, more preferably 5 to 30 wt from : . - "Styrene, alkyl acrylates and alkyl methacrylates built up.

Examples of acrylic components forming the crosslinked acrylic copolymer include alkyl acrylates, preferably those with 2 to 12 carbon atoms in the alkyl group, and alkyl methacrylates, preferably those with 1 to 4 carbon atoms in the alkyl group. Specific Examples of alkyl acrylates are 2-ethylhexyl acrylate, n-butyl acrylate, 2-methylbutyl acrylate, ethyl acrylate, n-hexyl acrylate and n-dodecyl acrylate. Specific examples "for ArKylmethacrylät are Meth3'lmethacrylat, Ethylmethacrylat and n-butyl methacrylate. Crosslinking agent, which can be used to crosslink the acrylic copolymers include, for example, ethylene glycol dimethacrylate, Diethylene glycol diacrylate, divinylbenzene and divinyltoluene. .

Examples of alkyl acrylates and methacrylates as Graft monomers for grafting onto the parent polymer may be the same as those given above with respect to the parent polymer. The graft monomer may contain a small amount of acrylonitrile.

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The elastonated acrylic-polymer copolymers and the processes for their preparation are known. You can, for example, by emulsion polymerization of 35 to 60 parts by weight of an alkyl acrylate, 5 to 20 parts by weight of butadiene and 0.1 parts by weight of an alkyl methacrylate in the presence of 0.6 to 1.3 parts by weight of a crosslinking agent, addition of a flocculant to the latex obtained for adjustment Its average particle acid diameter preferably to about 0.13 to 0.20 μm and grafting of the graft monomer onto the latex-type rubber obtained (parent polymer). The grafting can be carried out, for example, by graft polymerization of 20 to 25 parts by weight of a Mofioraergemisches of § to 15 parts by weight of styrene, 5 to 15 parts by weight of methyl methacrylate, 0 to 10 parts by weight of acrylonitrile and 0.1 to 0.3 parts by weight of a crosslinking agent as the first graft component with 65 parts by weight of the latex-like rubber (trunk polymer) and other graft-polymerizing 10 to 15 parts tines Monomergemischss from 10 to 15 parts by weight of methyl methacrylate u, nd Q _f 1 to 0.3 parts by weight of a Vernetzun, gsmittel! 5 aip second grafting be effected "

The above elastonated acrylic graft copolymers (D) and the methods for their preparation are detailed for example in d§p US-PS 3,842,144, 3,886,232 and 3,886,235 in which such graft copolymers as ModificierkQmppne.n.'tie are described. These Graft copolymers are available from ifandel and it can. Zuspielsvreise a sold under d @, r designation HIA-15 Resin from Kureha Chemical Industry Co., Ltd. obtain will.

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The polycarbonate resin compositions according to the invention can furthermore contain an olefin resin (E) derived from an olefin having 2 to 6 carbon atoms. Examples of such olefin resins are homopolymers of C _{2 to} C 6 olefins or copolymers of these with one another or with other olefins which can be copolymerized with the olefins Monomers such as vinyl acetate, vinyl chloride or tetrafluoroethylene Examples of preferred olefin resins are polyethylene, polypropylene and poly (4-methylpentene-1) Processes for producing these olefin resins are well known, and the olefin resins can be obtained commercially.

The polymethylpentene resins' (E) used in the masses of In the invention can be used, for example, polymers based on 4-methylpentene-1, preferably such with a density of about 0.83 to about 0.84. Such resins are commercially available, for example from Mitsui Petrochemical Industries, Ltd. under the name

Examples of polyethylene resins (E) are polyethylene low density, medium density polyethylene, high density polyethylene and suitable blends thereof »These Polyethylene resins are also commercially available. Polyethylene resins having a density of about 0.94 to about 0.96 'or mixtures thereof are preferred.

Suitable polypropylene resins (E) have a density of about 0.89 to about 0.91 and mixtures thereof will be used also preferred. These polypropylene resins are also commercially available. ;

Furthermore, isthylene / propylene copolymers, ethylene / Butene-1 copolymers, propylene / butene-1 copolymers and

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Ethylene / 4-methylpentene-i copolymers as examples of Olefin copolymers are listed. Examples of copolymers of such olefins with other copolymerizable ones Monomers are ethylene / vinyl acetate copolymers, Ethylene / vinyl chloride copolymers and ethylene / tetrafluoroethylene copolymers.

In the polycarbonate resin compositions according to the invention, _t is of larger proportions of the polycarbonate resin (A) and the aromatic polyester (B) and smaller proportions of the Isobutylencopolyinerkautschuks (C) and the elastomeric Acrylpfropfcopolymerharzes (D) and optionally the from a C £ - to Cg Olefin-derived olefin resin (E) are built up, the ratios of the individual components are the following:

(A) Polycarbonate resin: 20 to 90% by weight, preferably

AO up to 80 % by volume.

(B) Aromatic polyester resin: 5 to 70% by weight, above

preferably 10 to 45% by weight.

(C) Isobutylene copolymer rubber: 1 to 15% by weight, preferably 2 to 12 Qew.%,

(D) Elastomeric acrylic graft copolymer resin: 1 to 20 Gev /.%,

preferably 3 to 15% by weight. • (E) olefin resin: 0 to 15% by weight, preferably 0 to

10 wt.? I,

It is also required that, within the above ranges of the ratios, the weight ratio of [Resin (A) + Resin (B)] / [Rubber (C) + Resin (D) J from 2 to Is 20, and if the resin (E) is present, the weight ratio of resin (B) / [rubber (C) + resin (D) + resin (E)] is from 1 to 5.

If the proportion of the poly carbonate resin (A) is too low and is below the above lower limit

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the excellent impact resistance, especially the excellent impact resistance at low temperatures, and excellent resistance to impact resistance deterioration due to heat aging such as those of the The aims of the invention are not to be achieved. If the proportion is too large and above the upper limit, the desired excellent solvent resistance can be obtained cannot be obtained according to the invention.

If the proportion of the aromatic polyester resin (B) too low and below the lower given above Limit, the high rigidity and solvent resistance, as they represent the aim of the invention, are not. achieved. In case the amount is too big and is above the upper limit, the excellent can Impact resistance at low temperatures and the excellent resistance to damage to the Impact resistance through 1 ',' poor aging as the goal of the Invention cannot be achieved.

If the ratio of isobutylene copolymer rubber (C) is too low and below the above lower limit, the excellent solvent resistance and the excellent impact resistance (with a 6.35 mm thick sample) as intended according to the invention cannot be obtained. If on the other hand the value is too large and above that given above is the upper limit, the characteristic rigidity of the polycarbonate resin is drastically decreased and delamination occurs in the molded article in the resin composition and damages their appearance. ■

If also the proportion of the elastomeric acrylic graft copolymer (D) is too low and below the above

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specified lower limit, can be the excellent Impact resistance (especially at low temperatures) and the excellent resistance to Damage to impact resistance through heat aging, as is the aim of the invention, cannot be achieved. If the ratio is too large and above the upper limit, the melt flow rate will decrease Resin compound and various mechanical properties such as rigidity, tensile strength and flexural strength of the molded article made from the resin composition obtained are damaged.

The olefin resin (E) serves as an optional component to keep the excellent properties listed above in balance.

If the weight ratio of [Resin (A) + Resin (B)] / [Rubber (C) + Resin (D)] is too low and below the is the lower limit listed above, the Melt flow rate of the resin composition and the mechanical properties such as rigidity and flexural strength a molded article made of the resin composition are harmed. If the weight ratio is too high and above the upper limit, the excellent Impact resistance at low temperatures and the excellent resistance to damage to the Impact resistance through heat aging, as is the goal of Invention cannot be achieved.

Furthermore, if the weight ratio of resin (B) / [Rubber (C) + Resin (D) + Resin (E)] too low and below is the lower limit given above, the melt flow rate of the resin composition decreases and the rigidity of a molded article made from it

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that is reduced. If the value is too high and above is the upper limit, can have excellent impact resistance at low temperatures and the excellent resistance to damage to impact resistance cannot be preserved by heat aging.

In a preferred embodiment of the invention can be a polycarbonate resin composition with excellent solvent resistance, especially resistance to gasoline of high oetane number, an excellent one Impact resistance at low temperature, excellent resistance to damage to impact resistance due to heat aging, improved fluke properties and excellent mold releasing properties can be obtained in a well-balanced combination, following the test procedures given below a melt flow rate of about 10 to 15 g / 10 minutes, a flexural modulus of about -18_x 10 to ■ _ ■ '

3/2
22 10 kg'f / cm, a relative flexural strength in:

Gasoline with a high oetane number of about 65 to 80 _s, a relative flexural strength in carbon tetrachloride of about 70 to 90, no cracking in the screw clamp test in gasoline with a high oetane number, carbon tetrachloride or methyl isobutyl ketone, a releasability of no more than about 100 kg and in many cases no more than 90 kg in the mold release test, an Izo'd impact strength of at least about 50 kg-f «cm / cm (3.1S mm thick) in the impact resistance test at -1O ⁰ C and a -Warm me aging resistance (according to de-r \ v ^r ärmebehandlung) of at least 55 kg · cm / cm at blow heat aging test (125 C ⁰ χ 65 hours, 3.18 mm thick) include. A 6.35 mm thick test piece has an Izod impact strength at -10 ⁰ C of at least 20 kg f'cm / cm, and after the heat treatment at

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125 ^° C. for 65 hours it shows an Izod impact strength of more than 20 kg ^# f * cm / cm.

The polycarbonate resin compositions according to the invention can be prepared by mixing the polycarbonate resin (A), the aromatic polyester resin (B), the isobutylene copolymer rubber (C), the elastomeric acrylic graft copolymer resin (D) and optionally the olefin resin (E) using any known kneading equipment, by means of which these components can be mixed uniformly. For example, the four components (A), (B), (C) and (D) and optionally (E) may be mixed by a mixer such as a V-type mixer or a super mixer and then melt-mixed in an extruder melt-combined by a mixer such as a co-kneader. Components (C),. (D) and (E) ₁ the compo-

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components (c) and (D) and components (C) and (E) each by a mixer such as a kneading drum or a Banbury mixers are mixed and the resulting mixtures can be used in the molten state with the or the remaining components are mixed. Among these methods are those which have two or more melt blending operations are preferred because they increase the degree of mixing.

The melt blending can be effected at a temperature at which the component having the highest melting point can be melted. For example, the temperature is about 230 to about. 300 ⁰ C.

In addition to components (A), (B), (C) and (D) and optionally (E), the polycarbonate resin compositions according to the invention can contain various additives which are usually incorporated in resin compositions of this type. Derarti-; ge additives are for example 0.5 'to about 20 parts by weight of a filler or reinforcing agent, about-0.01 to about 0.1 part by weight of a heat stabilizer, about 0.01 to about 0.2 parts by weight of an antioxidant, about 0.1 to about 0.7 parts by weight of a light stabilizer, about 0.1 to about 10 parts by weight of a fire retardant, about 0.5 to about 3 parts by weight of a plasticizer, -, about 0.1 to about, 3rd weight.

parts of an antistatic agent, about 0.1 to about 1 Parts by weight of a mold release agent, about 0.3 to about 1 part by weight of a propellant, and about 1 to about 10 parts by weight of other resins or rubbers, which can be mixed with these components. The above amounts of the additives are based on 100 parts by weight of the polycarbonate resin. :

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Examples of fillers or reinforcing agents include glass fibers, asbestos, carbon fibers, silica, Talc and calcium carbonate.

Examples of heat stabilizers include triphenyl phosphite, Tris (2,6-dimethylphenyl) phosphite, tris (mixed mono- and di-nonylphenyl) phosphite, dimethylbenzene phosphonate and trimethyl phosphate.

Examples of antioxidants include octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] '.

Examples of light stabilizers include 2- (2-hydroxy-5-methy! Phenyl) benzotriazole, 2- (2-hydroxy-5-tert, octylphenyl) benzotriazole and 2-hydroxy-4-n-octoxybenzophenone.

Examples of fire retardants include 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, hexabromocyclododecane, Sodium 3,5-dibromobenzenesulfonate and sodium lauryl sulfate.

Examples of plasticizers include dioctyl-4,5-epoxy-hexahydrophthalate, Tris (octoxycarbonylethyl) isocyanurate, tristearin and epoxidized soybean oil.

Examples of antistatic agents include glycerol monostearate, Sodium stearyl sulfonate and sodium dodecylbenzenesulfonate.

Examples of mold release agents include stearyl stearate, Beeswax, contan wax and paraffin wax.

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Examples of other resins are polystyrene, polymethyl methacrylate, AS resin, ABS resin, MBS resin and polyphenylene oxide.

These additives can be added at an appropriate time during the mixing of the components to form the Cash register.

The following examples illustrate the invention

Farther. All parts in these examples are based on weight. The various properties reported in these examples were determined according to the

measured using the following procedure.

(I) Mold flowability. "- - :. -

Dried pellets of the l.'arse vrurden used as samples and the Sehmelzfließfähigkeit of the specimen was by the method fr.enäß ASTR D1 "238 genss-sen, -said""However," set the test temperature at 2SO ⁰ G and the test load β 2160 - was ". Larger values show better flowability.

(Ii) stiffness:

Dried pellets of the mass "were molded into a bending test specimen (127 mm χ 1?, 7 ram χ 6.35 mm). The test specimens were treated Wehrend 24 hours at a temperature of 23 ⁰ C and a humidity of 50% and then its flexural strength at 23 ⁰ C by means of a Zugmeßgerätes "(model TOH 5OQD Shinko Co., Ltd.). The flexural modulus of the specimens is determined from the Cr.anmmgs load curve. A higher flexural modulus indicates a higher rigidity,

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(Ill) Solvent Resistance

(Ill-a) Bending test in solvent

A flexure test specimen (127 mm 12.7 mm 0.35 mm) was molded from dried pellets using an injection molding machine. The specimen was treated at a temperature of 23 ^° C. and a humidity of 50 % for 24 hours. It was then immersed in high octane gasoline (manufactured by Showa Oil Co., Ltd.) or carbon tetrachloride (first grade reagent) for 15 seconds, and in this state, its flexural strength was measured with a tensile meter (Model TOM 500D manufactured by Shinko Co., Ltd.) .) measured. The solvent resistance was determined by the ratio of flexural strength (a) to flexural strength of 920 kg * f / cm ~ of a sample of the same size made from Fanlite L-1250 (name of bisphenol A-type polycarbonate, product of Teijin Chemicals Ltd.) ) was produced, rated in air [(a) / 920] χ 100. Higher ratios give better solvent resistance.

20 (III-b) screw clamp test

A flat plate of 127 mm × 127 × 3 mm was molded from predried pellets by means of an injection molding machine. Holes with a diameter of 6 mm were drilled in the plate by means of a drill, and the plate was ^{treated at a temperature of 23 Γ} ΐ and a humidity of 50 % for 24 hours. After the treatment, the plate was clamped with K6 screws and nuts with a torque of 70 kg «cm. The plate was immersed in the specified solvent for 5 minutes, allowed to stand in the air for 24 hours, and then examined for the occurrence of cracks.

BATH ORIGINAL

The absence of cracks indicates excellent solvent resistance.

(IV) impact resistance

Impact test specimens 64 mm 12.7 mm x 3.18 mm in size or 64 mm 12.7 mm 6.55 mm in size were molded from dried pellets of the mass using an injection molding machine and a notch of 0.25 mmR was formed in the test pieces. Each test piece was treated at a temperature of 23 ^° C. and a humidity of 50 ° C. for 24 hours, and then its impact strength was measured with an Izod impact tester (product of Toyo Seiki Co., Ltd.). Higher impact strength values indicate higher impact strength.

(IV-a) Impact resistance at low temperatures

The heartbeat test specimen formed in the above manner was left to stand in a constant temperature vessel at -10 ⁰ C for one hour and immediately afterwards removed from the vessel and tested for the impact resistance by means of the same Izod

_ Impact test device examined. Higher impact strength values indicate higher impact strength. :

(IV-b) Test for resistance to damage to the Impact resistance due to heat aging

The notched test specimen prepared according to the above (IV) was allowed to stand in a vessel of a constant temperature at 125 ⁰ C for 65 hours. Then it was removed from the vessel and kept at a temperature of 23 ^° C

and a humidity of 50 % for 24 hours. After the above heat aging treatment, the impact strength of the sample was measured by the above Izod impact tester. Higher impact strength values (kg · f · cm / cm) show a higher resistance to damage to the impact strength through heat aging.

(V) Mold Release Test

Pre-dried pellets were mm continuously cup-like Standen with a wall thickness of 4, a height of 20 now and a bottom diameter of 63 mm at a cylinder temperature of 270 ⁰ C and a mold temperature of 80 ⁰ C. The release mold load of a molded article obtained at the thirtieth thrust was measured by means of a strain gauge attached to the ejection plate of the mold. Lower mold release loads (kg) indicate better mold release capability.

Examples 1 to 6 and Comparative Examples 1 to 10

A predried polycarbonate resin was used in each experiment (Panlite L-1250, polycarbonate from bisphenol

2C Α-type from Teijin Chemicals, Ltd.) as component '(A), each the aromatic polyester resins listed in Table I below as component (B), the isobutylene copolymer rubber (IIR-065, a product of Nippon Butyl Co., Ltd.) as component (C) and an elastomer

25 acrylic graft copolymer (HIA-15, product of Kureha

Chemical Industry Co., Ltd.) as component (D) in the amounts shown in Table I by means of a V-type mixer to form the polycarbonate resin composition. The mass was then ^{melt-extruded at 280 °} C. using an extruder with a screw diameter of 30 mm (model VSK-30 from Chuo Kikai Co., Ltd.).

429.ν. ··, y

Test specimens were made by injection molding the obtained composition in the manner described above in connection with the preparation of the test specimens as described manufactured and tested for melt flow rate, flexural modulus, solvent resistance, impact resistance, Impact resistance at low temperatures and resistance to damage to impact resistance through ; Warning aging tested. The results are in Table I. contain.

Examples 7 to 14 and Comparative Examples 11 to 1 ^

Example 1 was repeated, but using each of the olefin resins listed in Table IT as a component . (E) in addition to the resin (A), the resin (B), the rubber- (C) and the copolymer (D), as described in Bei-. game 1 was used, was used.

The results are given in Table II »

The following abbreviations are used in Tables I and II below:

PET (a): polyethylene terephthalate (designation TR-2000 . . as a product of Teijin Limited) PET (b): polyethylene terephthalate (designation TR-R

of Teijin Limited)
PBT (c): polybutylene terephthalate (designation -CH-7-000

the "Teijin Limited)
25 HIBK: methyl isobutyl ketone

PKP: Polymethylpentene (designation RT-18-der.

Mitsui Petrochemical Industries ,, Ltd ") PE: polyethylene (designation Hizex 33OOF

Mitsui Petrochemical Industries, Ltd.) PP: Polypropylene (designation XK-I 5k der

Chisso Petrochemical Co., Ltd.)

BATH ORIGINAL

Table I.

Ver ι (A) Mass (parts) Art lot (C) (D) Melting Bending Solvent resistance CCl / Cracks in the screw
clamp test CCl, HIBK search 2 (B) river
Schwin- module
(x10 ³ kg.f / Relative bending
tensile strength petrol 3 αiffKeix
(g / 10
Min ^ cm ² ) in solution
medium (so 73 higher
Octane number 0 0 4th p _ET u; 20th 1 IXXl · J 3 gasoline higher 75 0 0 0 5 65 P _ET (b) 25th 5 10 Octane number 70 0 0 0 6th 60 Il 30th 5 10 11, 8 20.0 77 80 0 0 0 H
Q) 1 58 _PBT (C) 15th 5 7th 10.1 18.8 72 72 0 0 0 ■ Η
O ₁
T Γι 2 71 Il 23 7th 7th 10.5 18.6 68 86 0 0 0 ν J
• Μ
ω 3 55 Il 40 12th 10 11.9 20.2 76 9 0 X X pa 4th 50 - - 5 5 12.3 18.8 73 64 X 0 0 5 100 p _UT (c) 70 O O 13.9 21.4 77 57 0 0 X 6th 8th _PET (a) 3 8th 14th 8.5 • 22.3 50 14th 0 X X 7th 80 p _BT (c) 15th 7th 10 12.0 16.7 63 62 X 0 0 Q)
• Η 8th 80 Il U O 5 13.6 17.2 64 86 0 0 0 ω 9 60 _PET (a) 25th 20th Il 9.5 22.4 56 47 X 0 0 • Η
ω 10 70 _pET (b) Il 5 O .24.6 15.7 60 51 0 0 0 40 It 15th Il 30th 12.9 21, 1 78 88 0 0 0 ΰ
• Η
Π) 50 PBT ^KC) 26th 15th 20th 0.4 14.0 53 82 X 0 0 KLr
H
bO 70 Il 85 2 2 8.4 13.7 51 0 Sh 10 Il 3 12.3 22.3 71 6.6 22.8 73

i t

ti ff

Ca:

CJ

Table I (cont.)

Ver 1 at -10 ¹ C Izod impact strength (kgf / cm) Heat aging at 1 25 ⁰ C for 65 hours. Do that
treatment Thickness 6.35 mm
(1/4 "thick) After
treatment Free form search 2 thickness
3.2 mm
(1/8 "thick) Thickness 3) 2 min
(1/8 "thick) 50 Before the
treatment 49 gaoeiasx
(kg) 3 33 thickness
6.35 mm
(1/4 "thick) Before the
treatment 69 55 53 4th 31 28 81 50 60 A 6 70 H 5 29 25: 79 70 57 60 75 φ
• Η 6th 77 22nd 71 45 73 22nd 90 pi 1 25th ^; 36, . 85 69 68 54 70 Be 2 23 24 84 . 7th 63 -Λ 75 3 84 22nd 83 8th 1.4 '. VJl 100 4th , 4: ■ 12 95 ,, 66 , 4 48 100 VJl 29 2 β ■, ■, .80 ■ 54 VJI - (H 6th 89 18th 71 9 - 73 ON 100 7 .. 11th 17th 94 11th 52 13th 100 ■ • -ι ¹ 8th 12 ■. ■ 11th 87 49 , 84 17th 100 , Ω
W.
Γ! 9 , 20 12th 26th 57 28 35 - ϋ
-H 10 ;. π ■; 11th 62 67 ' 46 17th - Φ
ri 20th 12., 66 VJI 77 4th 1 00 H
G) . ■■ / ■■ ^Λ '- ^'11 ■. ■ ' 93 5 - 4, ■ ;; -β. ■. -

Table II

Ver H
Φ 7th Mass (parts) (A) (B) Art lot (C) (D) . (E) lot ochmelz-
river
Schwin-
dirity Be-
P ^- -UTIfS- Solvent resistance CCl ₄ Cracking at
Screw clamp CCL ₄ MIBK search • rl 8th 74 FBT ^c) 15th 3 Art Mm.) Cj ^ * ro ~
module Relative j
resistant. 80 test 0 0 • Η
ω 9 60 Il 25th 5 PMP 3 • f / crn ^ *) 3ie-
Leasiness 86 3enzin
higher
Octane number 0 0 CQ 10 56 Il 35 2 5 Il 5 10.5 in the solution
medium - (JS) 83 0 0 0 11th 6ί, Il 20th 5 Il Il 2 14.2 20.6 petrol
higher
Octane number 73 0 0 0 "" I.
(Λ
si
OH 12th 57 (I. 30th 3 M. PE 4th 13.1 21, 2 72 73 0 0 0. • Η (D
OH 13th 60 PET ^a; 25th 5 Il Il 3 11.0 19.9 73 79 0 0 0 HP.
bfW 14th 62 Il 20th 5 7th FMP 5 10.2 19.9 79 70 0 0 0 ω ω 11th 67 PBT ⁰ ^ 20th 5 5 PE 5 12.2 18.6 71 72 0 0 0 12th 52 PBT ^{C /} 20th 3 8th PP 3 10.1 19.5 71 68 0 0 0 13th 57 PET ^b) 15th 3 5 PMP 20th 10.6 18.6 76 59 0 0 0 14th 50 PBT ^C ) 20th 10 5 PE 20th 11, 6 20.2 68 69 0 0 0 Il PET ^b) 44 2 5 ti 10 8.3 16.1 70 88 0. 0 0 10 PMP 2 12.8 15.5 73 0 2 15.0 . 17.9 59 0 21, 8 70 78

«« C

• * ·

4 C

Table II (cont.)

0,

Ver H
Φ 7th at -10 ⁰ C thickness
6.35
(1/4 " Izod impact strength , Heat aging (kg f / cm) 68 70 > Thickness 6.35 mm
(1/4 "thick) After
treatment Shape free search • Η
Oil 8th thickness
3.2 mm
(1/8 "thick) 55 Thickness 3.2 mm
(1/8 "thick) at 1 , 75 ■ 66 Before the
treatment . , .64 fork load
(kg) • Η
03 9 76 24 mm
thick) Before the
treatment 25 ^C C for 65 hours 81 47 71 52 45 cq 10 32 25th 86 . · ■ 37;. ■ 74 61 58 55 11 23 36 70 i \ ^: oh the
treatment 90 62 66 59 70 ι
OT 12th 77 · 24 67, , 79 59 71 57 50 QH 13th 31 24 85 ,, 82 60 62 ... 47 60 φ · Η
H Ά 14th 32 27 89 65 61 57 50 Forg
by S 1 1 ',' "25 23 25th 64 56, 45 12th 28, , 16 35 : 69 . 27 60 13th 17th 16 36 31 10 40, 14th : 15 , 13 ¹ 3 63 25th 35 22nd 53 ; 15th 35 1 2 51

• i

cn

CD

Claims (5)

MONKS DR. E. WIEGANDt (1932-1980) DR. M. KOHlER DIPl.-ING. C. GERNHARDT HAMBURG DIPl.-ING. ). GLASSES DIPL-ING. W. NIEMANN OF COUNSEL '* Wl EGAND * * * N IEMANN * KÖHLER GERNHARDT GLAESER PATE NTANWKtTE Eutopeon Potent Attorney » W. 44283/82 - Ko / Hi TELEPHONE: 089-555476 / 7 TELEGRAMS: KARPATENT TElEX ι 529068 KARP D D-8000 MÖNCHEN 2 HERZOG-WILHEIM-STR. Λ6 December 8, 1982 Teijin Chemicals, Ltd, Tokyo (Japan) Polycarbonate resin composition Claims .1. Polycarbonate resin composition consisting of (A) 20 to 90% by weight of a polycarbonate resin, (B) 5 to 70% by weight; of an aromatic polyester resin, (C) 1 to 15% by weight of an isobutylene copolymer rubber, which consists of a larger proportion of isobutylene and a small 1C is composed of isoprene, (D) 1 to 20% by weight of an elastomeric acrylic graft copolymer resin, that of a crosslinked acrylic copolymer with a content of not less than 3% by weight of butadiene as comonomers, which is free from ethylene, as the parent polymer and at least one graft monomer grafted thereon BATH from the group of styrene, alkyl acrylates and alkyl methacrylates is constructed, and (E) 0 to 15 wt.% Of a derived from an olefin having 2 to 6 carbon atoms, the olefin resin, where the weight ratio of [resin (A) + resin (B)] / [Rubber (C) + Resin (D)] is 2 to 20 and, if the resin (E) is present, the weight ratio of Resin (B) / [rubber (C) + resin (D) + resin (E)] is 1 to 5. 2. Composition according to claim 1, d a d u r c h characterized in that the polycarbonate resin (A) from a dihydric phenolic component, which consists mainly of 2,2-bis (4-hydroxyphenyl) propane, is a derivative of polycarbonate. 3. Composition according to claim 1 or 2, characterized in that the aromatic polyester resin composed of an alkylene glycol having 2 to 10 carbon atoms and an aromatic dicarboxylic acid with 8 to 12 carbon atoms or an ester-forming derivative thereof polyester. 4. Composition according to claim 1 to 3, characterized in that the parent polymer des Acrylic copolymers (D) is a polymer with an average particle diameter of 0.13 to 0.20 μm and from 35 to 60 parts by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group, 5 to 20 Parts by weight of butadiene, 0 to 10 parts by weight of an alkyl methacrylate having 1 to 4 carbon atoms in the Alkyl group and 0.6 to 1.3 parts by weight of a crosslinking agent derives while the graft monomers from consists of a mixture of styrene and methyl methacrylate. BATH ORIGINAL 5. Composition according to claim 1 to U, since you rch characterized in that the Isobutylencopoly · ^ merkautschuk (C) consists of 93 to 99 wt.% Isobutylene and 7 to 1 wt.% Isoprene copolymer rubber.